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  • Polymer and Materials Science  (2,271)
  • Organic Chemistry  (1,351)
  • PROPULSION SYSTEMS  (208)
  • 1980-1984
  • 1960-1964  (3,830)
  • 1925-1929
  • 1963  (2,162)
  • 1961  (1,668)
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  • 1980-1984
  • 1960-1964  (3,830)
  • 1925-1929
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  • 1
    Electronic Resource
    Electronic Resource
    High molecular weight poly-L-proline: Synthesis and physical-chemical studiesThis is “Polypeptides. XLI.” For the preceding paper in this series see A. J. Alder, G. D. Fasman, and E. R. Blout, J. Am. Chem. Soc., in press.This work has been supported by the Office of the Surgeon General, Department of the Army.Presented in part at the 132 Meeting of the American Chemical Society, New York, New York, September 1957. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 3-14 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-L-proline in the molecular weight range 50,000-90,000 has been synthesized from L-proline-N-carboxyanhydride. The molecular weight obtained is dependent on the initiator concentration. The rate constants for the polymerization have been determined by measuring the CO2 evolution. By observation of rotation during the polymerization, it is possible to deduce the conformation of the polymer in the polymerization solution. It is concluded that the immediate product of the polymerization is neither pure form I nor pure form II. The differences between form I and form II of poly-L-proline have been further characterized by measurements of their ultraviolet rotatory dispersion and their ultraviolet spectra.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360010103
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  • 2
    Electronic Resource
    Electronic Resource
    Modification of the reactivity of a small molecule by reversible association with a synthetic polymer. Inhibition of the hydrolysis of cationic esters by polyanionsAbstracted in part from a Ph.D. thesis to be submitted by J. A. Shafer to the Graduate School, Polytechnic Institute of Brooklyn, in June 1963. Financial support of this work by the Office of Naval Research and the National Institutes of Health is gratefully acknowledged. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 71-77 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The base-catalyzed hydrolysis rate of the cationic esters obtained by quaternization of N,N,N′,N′-tetramethylethylenediamine with phenylbromoacetate was studied in buffers and in solutions of partially neutralized polymeric acids. The polyanions were found to be powerful inhibitors of the reaction. This effect was interpreted as due to the association of the ester with the polyanion, from which the catalytically active hydroxyl groups are repelled. It is shown that kinetic data may be interpreted by a procedure similar to the Lineweaver-Burk plot to yield the reactivity of the bound ester and the dissociation constant of the polymer-ester complex.
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    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360010108
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  • 3
    Electronic Resource
    Electronic Resource
    Copolymers of L-proline and sarcosine: Synthesis and physical-chemical studiesThis is “Polypeptides. XLIII.” For the preceding paper in this series see E. R. Blout, J. P. Carver, and J. Gross, J. Am. Chem. Soc., 85 (1963).Presented in part at the 132 Meeting of the American Chemical Society, New York, September 1957.This work supported by the Office of the Surgeon General, Department of the Army. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 99-109 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of high molecular weight copolypeptides of L-proline and sarcosine have been synthesized. Experimental evidence is presented which indicates that the products are true copolymers rather than mixtures of homopolymers. In contrast to poly-L-proline I, a copolymer of L-proline-sarcosine I containing approximately 50% sarcosine is soluble in water. Two molecular conformations of the copolymers, similar to those found for polyproline, have been characterized by means of infrared spectroscopy and optical rotatory dispersion. The residue rotation of L-proline has been obtained from the copolymers and is -250°.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360010202
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  • 4
    Electronic Resource
    Electronic Resource
    Editorial (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 1-1 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360010102
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  • 5
    Electronic Resource
    Electronic Resource
    Theory of the helix-coil transition in DNA considered as a copolymer (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 25-32 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grand-partition-function theory of the preceding paper is used to derive expressions for the number of base pairs bonded in DNA with explicit consideration of the copolymeric nature of the DNA. The following features of the DNA molecule are taken into account: (1) the DNA's from different sources have different ratios of a-t and g-c pairs; (2) the a-t pair is weaker than the g-c pair; (3) the nearest-neighbor frequencies of the two kinds of base pairs are nonrandom; (4) the stacking energies (nearest-neighbor energies) of the various combinations of pairs may be different. An ensemble is constructed in which the features (1) through (4) are introduced by means of statistical weights on the various pairs and combinations of pairs, and an expression for the corresponding partition function is written. Expressions are derived for the number of bonded base pairs and the number of helical sequences.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360010105
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  • 6
    Electronic Resource
    Electronic Resource
    Masthead (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963) 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360010201
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  • 7
    Electronic Resource
    Electronic Resource
    The presence in collagen of γ-glutamyl peptide linkagesSupported by grants from the National Institutes of Health, U. S. Public Health Service, A-3172, H-4762, H-3838, M-2565, M-2562. The material in this paper is taken from a thesis submitted by Carl Franzblau in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Sue Golding Graduate Division of Medical Sciences, Albert Einstein College of Medicine, Yeshiva University. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 79-97 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for formation of hydroxamic acids by direct coupling, in aqueous medium, of hydroxylamine hydrochloride and the sodium salt of a carboxylic acid. The reaction is mediated by a water-soluble carbodiimide, 1-cyclohexyl-3-[2-morpholinyl-(4)-ethyl]-carbodiimide metho-p-toluene sulfonate. Using model compounds, the production of α-, β- and γ-acyl hydroxamic acids was studied. Hydroxamic acid derivatives of α-polyglutamic and γ-polyglutamic acids were also prepared. Dinitro-phenylhydroxamate derivatives were prepared and subjected to Lossen rearrangement, and the reaction mixtures hydrolyzed. Analysis showed that α-polyglutamic acid yielded as many molecules of α,γ-diaminobutyric acid as there had been glutamic acid residues in the form of the dinitrophenylhydroxamate, and gave rise to no ammonia and succinic semialdehyde. In contrast, γ-polyglutamic acid yielded exactly twice the molar quantity of ammonia as there had been glutamic acid residues in the form of dinitrophenylhydroxamate, and also gave rise to significant quantity of succinic semi-aldehyde but no α,γ-diaminobutyric acid. Since production of the latter is characteristic of α-glutamyl hydroxamates and production of the former is associated with γ-glutamyl hydroxamates, the results indicated that the side-chain carboxyl groups of either polymer retained their identities during formation of the hydroxamic acid derivative, and no interchange had occurred between α- and γ-carboxyl groups. These methods were then used to establish that gelatin of ichthyocol contains (per 1000 total residues) at least 20 residues of glutamic acid in γ-peptide linkage. Due to the incomplete dinitrophenylation of the hydroxamic acid derivative of the protein, gelatin of calf skin collagen gave a lower figure of 10 such linkages per 1000 total amino acid residues-a value which must be considered a minimum value. These results show that γ-glutamyl peptide bonds exist in collagen.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360010109
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  • 8
    Electronic Resource
    Electronic Resource
    Theory of helix-coil transitions involving complementary poly- and oligo-nucleotides. I. The complete binding caseThis investigation was supported in part by Research Grant A-4283 from U. S. Public Health Service.Based upon a portion of a Ph.D. thesis to be submitted by W. S. M., Jr., to Brown University. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 133-143 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A statistical thermodynamic treatment of thermally induced helix-coil transitions is formulated with the matrix method for an (ensemble) of system(s) in which one strand of a double helix consists of a homopolymeric polynucleotide and the other strand comprises a number of complementary oligonucleotides. Each oligonucleotide is considered to be completely bound to the longer chain when in the helical configuration and completely free from it when in the randomly coiled configuration. The case of partial binding; i.e., “dangling,” is treated in a later paper. Taken into account in both cases are intrachain “stacking” interactions between nearest neighbor residues and interchain hydrogen bonding.An approximate treatment of the characteristic equation of the formulation indicates that the reciprocal of the transition temperature (1/T0) is a linear function of the reciprocal of the degree of polymerization (D.P.) of the oligonucleotides. In the same approximation, 1/T0 is also a linear function of the negative logarithm of the absolute activity of the oligonucleotides. Transition curves obtained by exact calculation on a computer are presented for various degrees of polymerization of both the oligo- and polynucleotides. These curves show a sharpening of the transition with increasing D.P. of the long chain and the aforementioned reciprocal D.P. dependence of 1/T0.
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    URL: http://dx.doi.org/10.1002/bip.360010204
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  • 9
    Electronic Resource
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    Dielectric dispersion of polyglutamic acid solution (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 171-182 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric dispersion of polyglutamic acid (PGA) was studied in the pH range of 4-9.8. Three different dispersion curves were obtained. Above pH 6.0, where PGA has a random coil configuration, the dielectric dispersion is characterized by a large dielectric increment (ca. 450) and a relaxation time of 10-12.7 × 10-6 sec. Between pH 6.0 and 5.0, where PGA is in a transitional state with small viscosity, a dispersion curve with very small dielectric increment and also small relaxation time was observed. Below pH 5.0, where PGA has a helical configuration, the dispersion is characterized by a relaxation time of 10-12 × 10-6 sec. and a dielectric increment of about 120. The dipole moment of coil and helical forms of PGA were calculated by using Allgen's equation, and qualitative discussions of these dielectric properties are presented.
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    URL: http://dx.doi.org/10.1002/bip.360010207
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  • 10
    Electronic Resource
    Electronic Resource
    Absorption spectra of nucleotides, polynucleotides, and nucleic acids in the far ultraviolet (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 193-208 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ultaviolet absorption spectra down to 185 mμ are presented for a number of nucleic acids and synthetic polynucleotides in the helical and random forms, and of their constituent mononucleotides, as well as the corresponding nucleosides and free bases. A short wavelength absorption band is in all cases observed with a maximum varying between about 187 and 201 mμ. These bands are more intense than those near 260 mμ. The helical polymers show a hypochromic effect in this region of a somewhat similar magnitude to that in the 260 mμ region. Other spectral phenomena accompanying denaturation and degradation are described.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360010302
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  • 11
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    The inactivation of soluble ribonucleic acid by formaldehyde (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 209-229 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The inactivation of sRNA by reaction with formaldehyde has been reported as it occurs under various conditions giving differing amounts of secondary structure. The theory of inactivation of an active macromolecule by a chemical reaction is developed. Results obtained with a partially melted out secondary structure show that formaldehyde inactivates sRNA by a single reaction at any one of about ten sites, while reaction at other sites does not affect the activity of the sRNA. In the presence of Mg++ at neutral pH, a large proportion of the active molecules are completely protected against inactivation. From the correlation between the amount of secondary structure and the difficulty of inactivation, it is shown that at least a portion of the secondary structure of sRNA is essential to its amino acid acceptor ability. A comparison of results of various workers shows that formaldehyde does not alter RNA as drastically as other reagents and thus enables more discrimination between sites of reaction which are essential and those which are not essential to biochemical activity.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/bip.360010303
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  • 12
    Electronic Resource
    Electronic Resource
    Editorial (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 295-295 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360010402
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  • 13
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    Infrared spectra and molecular conformations of D,L-copoly-γ-benzylglutamates (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 297-317 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared absorption and x-ray diffraction measurements have been made of D,L-copoly-γ-benzylglutamate fibers (cast from dioxane solutions) with various D/L ratios and with various degrees of polymerization. It was found that each chain of these copolymers consists of a random coil portion and an α-helix portion and that the conformation of the latter is similar to the α-helix of pure poly-γ-benzyl-L-glutamate. It was also found that the fraction of the α-helix portion increases with the degree of polymerization of the copolymer. A simplified polymerization mechanism has been proposed for mixtures of D- and L-amino acid N-carboxyanhydrides. A model of the molecular conformation of the D,L-copolypeptide chains derived from this proposed polymerization mechanism is in good agreement with infrared, x-ray, and other measurements. Based on the results of these observations, we discuss the number of L- or D-residues linked in succession that is required for initiating the formation of an α-helix during the course of polymerization.
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    URL: http://dx.doi.org/10.1002/bip.360010403
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  • 14
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    Optical properties of the poly-L-proline and collagen helicesThis research was supported in part by U.S. Public Health Service grants A5852 and 9202. Contribution No. 232 of the Graduate Department of Biochemistry, Brandeis University, Waltham 54, Massachusetts. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 319-330 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-L-proline I and II, polyphydroxy-L-proline II, polysarcosine, and collagen, as well as two model amides have been examined by far ultraviolet spectrophotometry. Absorption spectral data are presented. Neither in solution nor in oriented films of poly-L-proline I and II is there any indication of excition resonance splitting of the peptide absorption band. In collagen there is some, in the poly-L-prolines only minimal, hypochromicity. These observations, at least in poly-L-proline II, run counter to theory. Optical rotatory dispersion measurements in the ultraviolet indicate simple dispersion in collagen and poly-L-proline II down to at least 232 mμ. The Cotton effect (trough at 233 mμ) observed in α-helical polypeptides and proteins is absent. The implications of these findings are discussed.
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    URL: http://dx.doi.org/10.1002/bip.360010404
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  • 15
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    Dilatometric and refractometric studies of the helix - coil transition of poly-L-glutamic acid in aqueous solutionThis work was supported by grants from the U. S. Public Health Service (GM-K3-3441, GM-10880, HE-06285). (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 359-370 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix - coil transition of poly-L-glutamic acid (PGA) in aqueous solutions was followed by volume changes, ΔV, and also differential refractive indices, Δn. The increase in ΔV or decrease in Δn upon mixing the sodium salt of PGA with dilute HCl gave three straight lines between pH 7 and 4, the two breaks corresponding to the transition zone observed by other physical methods. For the reaction: —COO- + H+ → —CO-OH, ΔV per mole of H+ bound was 11.4 and 11.1 ml. in 0.01 and 0.2M NaCl solutions, respectively. An additional conformational change of about 0.5-1 ml. per amino acid residue was observed for the reaction: coil → helix, after taking electrostatic interaction into consideration. This was probably due to the release of the water of hydration at the amide linkages when the polypeptide coil is converted into the α-helix, or even the occurrence of voids in the polypeptide chain as a result of imperfect packing of the atoms, although the origin of this volume change is still not fully understood at the present time. The volume changes as calculated from Δn by assuming a constant polarizability of the polymer was found to be higher for the association reaction than those mentioned above. On the other hand, the calculated ΔV for the transition was in fair agreement with those by direct measurements.
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    URL: http://dx.doi.org/10.1002/bip.360010408
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  • 16
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    Optical properties of chromophore-macromolecule complexes: Absorption and fluorescence of acridine dyes bound to polyphosphates and DNAThe work described in this paper was sponsored in part by the U. S. Atomic Energy Commission and in part by the Department of Chemistry, University of California, Berkeley, California. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 401-417 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dye-macromolecule complexes provide good models for the study of the effects of coupling between chromophores. In addition to modifications of the visible and UV absorption spectra of the dyes at small interchromophore distances, very efficient energy transfer has been demonstrated at longer distances. The probability of nonradiative transition increases with the number of excitation transfers so that an array of oscillators close to one another becomes nonfluorescent. The insertion of a dye molecule, acting as a trap for the excitation energy, in the highly ordered system of chromophores constituted by the purine and pyrimidine bases of native DNA has given results supporting the intercalation model of Lerman and providing an experimental approach to the problem of the path length of energy migration in the DNA molecule. The average excitation path length seems to be of the order of only ten base pairs, a result which can explain the lack of fluorescence of the DNA.
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    URL: http://dx.doi.org/10.1002/bip.360010502
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  • 17
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    Sedimentation and diffusion of polyelectrolytes. Part II. Experimental studies with poly-L-lysine hydrohalides (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 473-495 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sedimentation, diffusion, and osmotic behavior of poly-L-lysine hydrochloride is examined over a wide range of ionic strengths and in solutions which range in relative composition from a swamping excess of added salt (suppression of charge effect) to salt-free solutions (maximum effect). The charge effect is found to essentially obey the theoretical treatment proposed in Part I of this work. The frictional coefficient of the macroion in salt-free solutions is comparable to that of the fully stretched chain. In excess of salt the friction is appreciably smaller, its magnitude not varying greatly with ionic strength. The molecular weight is determined osmotically and also from diffusion-sedimentation, with the charge effect suppressed by addition of salt or eliminated through the use of non-ionized forms of the polymer; a reasonable agreement is obtained between the methods. The influence of small ions on sedimentation is also examined. The secondary salt effect is found to be much smaller than that predicted theoretically; on the other hand, the substitution of different counterions in the absence of secondary salt effect gives rise to changes of the expected magnitude.
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    URL: http://dx.doi.org/10.1002/bip.360010506
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  • 18
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    The initial reaction in strong-base catalyzed polymerizations of α-amino acid N-carboxyanhydrides (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 500-502 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360010508
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  • 19
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    Properties of poly-β-hydroxybutyrate. I. General considerations concerning the naturally occurring polymerPortions of this work were taken from a thesis by R. Alper submitted to the Graduate School, Syracuse University in partial fulfillment of the requirements for the degree of Doctor of Philosophy. Presented before the Polymer Division at the 145th National American Chemical Society Meeting, New York, September 1963. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 545-556 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-β-hydroxybutyric acid has been isolated from two bacterial sources by two different procedures. Molecular weight and intrinsic viscosity for the two samples were vastly different. This was blamed on degradation occurring during polymer isolation. An optical rotatory dispersion curve for the high molecular weight sample showed a sharp increase in specific rotation at wavelengths less than 450mμ. From this fact and the reported optical activity of the monomer it is concluded that the polymer is stereo-regular. X-ray examination of the “native” and “regenerated” polymer yielded the same crystalline pattern. Electron diffraction and x-ray data on single crystals of the polymer indicate a fiber repeat of 5.9 A. The value can only be reconciled with some kind of helical conformation in the solid state.
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    URL: http://dx.doi.org/10.1002/bip.360010605
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  • 20
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    Studies of the conformation of amylose in solutionPaper presented in part before the Division of Carbohydrate Chemistry, 140th Meeting of the American Chemical Society, Chicago, September 1962. This work was supported by a Grant from the Corn Industries Research Foundation. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 527-544 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been suggested previously that water is a nearly indifferent solvent for amylose on the basis that the exponent a of the Mark-Houwink equation is very nearly 0.50 and the second virial coefficient A2 is extremely small. It is shown that such solutions do not show the expected precipitation on cooling and the temperature coefficient of the intrinsic viscosity is small and negative. It is suggested that water is both an indifferent and a nearly athermal solvent for this polymer. Various lines of evidence suggest the polymer to exist as a very stiff coil in this and in other solvents. Variations in the intrinsic viscosity and radius of gyration in various solvents show the importance of skeletal effects in addition to the usual osmotic effects. Application of the Porod-Kratky wormlike coil model leads to unreasonably short persistence lengths if the contour length is based on a fully extended conformation but large and reasonable values of the order 40-70 A. if it is assumed that the basic conformation is the helical one observed in various amylose complexes in the crystalline state. As was previously known, the specific optical rotation decreases sharply in aqueous solutions above approximately pH 12. Accompanying this change in rotation there is first a decrease, then an increase in intrinsic viscosity. This later behavior is strikingly reminiscent of the known behavior of polyglutamic acid in the pH-dependent transition from helix to coil. It is concluded that the conformation is that of a stiff coil with essentially helical backbone contour in neutral solution, and the decrease in rotation and in intrinsic viscosity at high pH results from a partial breakdown of the helical structure with a concomitant increase in backbone flexibility. The increase in viscosity and radius of gyration in extreme alkaline solution is probably due to a polyelectrolyte expansion of the polymer coil. Some other miscellaneous observations which are in accord with this model are also pointed out.
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    URL: http://dx.doi.org/10.1002/bip.360010604
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  • 21
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    Masthead (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963) 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360010501
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    Effect of hydrophobic bonding on the stability of poly-L-alanine helices in water (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 419-429 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Lifson-Roig theory for the helix-random coil transition in polyglycine has been modified to take side-chain interactions into account. The modified theory is developed specifically for poly-L-alanine which probably contains a β1-α4 hydrophobic bond. A conditional probability, expressing the strength of such a hydrophobic bond, is evaluated from the Nemethy-Scheraga data for the free energy of formation of the bond. This, together with the conditional probabilities for the states of the backbone chain, permit an evaluation of the partition function and properties of the helix-random coil transition. It is seen that the hydrophobic bond renders the poly-L-alanine helix much more stable than the corresponding polyglycine one, in agreement with data obtained by Gratzer and Doty.
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    Polynucleotides. VI. Molecular properties and conformation of polyribouridylic acidThe last paper in this series was by J. R. Fresco and J. Massoulié, J. Am. Chem. Soc., 85, 1352 (1963).This investigation was supported by grants from the National Science Foundation, the United States Public Health Service, and the American Heart Association. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 431-446 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical, hydrodynamic, and titration properties of polyribouridylic acid (poly U) were investigated in 0.2M Na+, pH 6. Above 15°C., poly U was shown to be a randomly coiled single chain, devoid of secondary structure. There is no shear rate dependence of viscosity; molecular weight is independent of ionic strength; there is virtually no conformationally dependent hypochromicity; no anomalous optical rotatory dispersion; and no anomalous titration behavior. The dependence of the sedimentation constant and intrinsic viscosity on molecular weight was determined. Poly U was shown to be the most highly expanded of all synthetic and naturally occurring randomly coiled polynucleotides.
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    Masthead (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360010601
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    Synthesis of poly-L-lysine and poly-L-lysyl albumin via ∊,N-trifluoroacetyl-α,N-carboxy-L-lysine anhydrideThis investigation was supported in part by research grants (AI-04715 and 235103) from the National Institutes of Health, United States Public Health Service. (1963)
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 517-525 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free poly-L-lysine base has been synthesized from ∊,N-trifluoroacetyl-α,N-carboxy-L-lysine anhydride via poly-∊,N-trifluoroacetyl-L-lysine (IV). No racemization occurred during the removal of trifluoroacetyl groups from IV with 1M piperidine. Measurements of optical rotatory dispersion suggest that IV exists in methanol in a helical form. The synthesis of poly-L-lysyl rabbit serum albumin is also described.
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    URL: http://dx.doi.org/10.1002/bip.360010603
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    Single point determination of intrinsic viscosity (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S30 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1963.070070436
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    Stress relaxation in molten polymers. III (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1673-1677 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The parabolic law, according to the equation , of the elasticity in the relaxation phenomena of molten polymers can be deduced from the consideration of the feature that the experimental stress relaxation curves show log-log plots which are often linear in a broad field. A general analysis, only on the basis of the viscoelastic equation permits calculation of relaxation functions, which are suggested as possible means of polymer characterization.
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    URL: http://dx.doi.org/10.1002/app.1963.070070509
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    The use of tensile measurements in following cellophane degradationThis work was carried out for the National Aeronautic Space Administration under contract NAS-5-2860. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1691-1695 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Comparisons were made of changes in molecular weight and in tensile strength of regenerated cellulose after exposure to 40% KOH at 90°C., for varying lengths of time. In the absence of air, both parameters decreased in a fairly consistent manner. In the presence of air, an initial steeper drop was followed by an irregular up-and-down pattern. The theory is advanced that the increase in tensile strength was caused by increased crystallinity.
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    Sorption of liquids by wool. Part IV. Sorption of ethanol by modified wool (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2053-2066 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Experimental results for the sorption of liquid ethanol by a variety of modified wools are described. Even slight changes in the chemical and physical structure of wool produced large changes in ethanol sorption rate. Blocking of amino groups decreased the sorption rate due to removal of primary sorption sites, but, surprisingly, carboxyl group modification greatly increased the rate. Modification of disulfide crosslinks increased the rate, while in most cases surface modification decreased it, which is contrary to expectation if a surface barrier to diffusion of penetrants is assumed. Theories are advanced for the observed changes in sorption properties and for the small changes found when water if used as sorbate. Saturation sorption values showed only slight changes from that for untreated wool. The largest increases resulted from disulfide bond modification, which is explained as due to lower resistance of the treated wool to swelling forces, allowing greater swelling and sorption.
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    URL: http://dx.doi.org/10.1002/app.1963.070070608
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    Performance of a versatile variable-volume permeability cell. Comparison of gas permeability measurements by the variable-volume and variable-pressure methods (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2035-2051 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: An improved cell which permits the measurement of permeabilities of membranes to gases over a wide range of temperatures and gas pressures is described. The measurements are made by the variable volume method, under constant pressure differential across the membrane. The cell lends itself particularly well to routine tests, because it does not require calibration or the use of vacuum techniques. The performance of the cell is discussed, and typical experimental results are presented. A modified permeability cell of the same type for high-pressure studies is also described. Measurements with this apparatus show that the rate of gas permeation obeys, in some cases, a single from of Fick's law, even under pressure differentials across the membrane as high as 800 psi (54 atm.). The paper also compares permeability data obtained by the variable volume and the variable pressure methods. The permeability of 0.002 in.-thick Alathon 15 polyethylene to oxygen and nitrogen was determined between 0 and 50°C. by the two methods, using the same sample of membrane in situ, and the measurements were found to agree within experimental error. Permeabilites of 0.010 in.-thick samples of Alathon 15 polyethylene to nitrogen, oxygen, helium, and carbon dioxide obtained in the same temperature range by the variable volume method were 15-30% higher than the corresponding data determined by the variable pressure method. This discrepancy could be due to the fact that the variable pressure measurements with the thicker membrances may not have been made under true steady-state conditions, although permeabilities were determined from apparently linear sections of permeated gas pressure vs. time curves. A critical re-examination of the methods used to determine permeability constants is suggested.
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    Friction and deformation of nylon. II. Theoretical (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2105-2120 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: It was concluded in the preceding paper that there was a significant difference between the indices m and n in the expression A = βWm and F = αWn by which the contact area A and the friction F were found to be related to the load W when nylon 610 slid on glass. A discussion of published adhesion theories of the friction of elastic bodies shows that the difference n - m is too small to be attributed to roughness of the nylon surface. It is concluded that under the contact pressures used the nylon surface was effectively smooth and that the friction of a unit area of “true” (i.e., molecular) contact between nylon and glass increased with pressure P as about P1/4. A theoretical treatment is given of the dependence of friction on load for a rough-surfaced elastic body which covers the load range in which the surface asperities become completely flattened. It is shown that from measurements of the elastic properties of the body and feasible measurements of its surface texture one can estimate the load at which the dependence of friction on load changes from that for a rough to that for a smooth surface. Comparison with a published experiment is satisfactory.
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    Friction and deformation of nylon. I. Experimental (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2075-2103 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: An apparatus which permits the simultaneous measurement of kinetic friction and contact area between polymer hemispheres and a smooth glass surface has been used to study the dependence of friction and contact area on load, specimen radius, sliding speed, and loading time. Hemispherical nylon 610 specimens of radii 0.12-0.58 cm. have been used with loads of 0.7-200 g. and sliding speeds from 10-7 to 3 × 10-2 cm./sec. All measurements were performed in air at 20°C. and 66% r.h. The contact area was estimated from optical interference fringes (Newton's rings) between the surface of the specimen and that of the glass plate, by means of a theoretical expression, experimentally verified, for the shape into which an elastic hemisphere is deformed when pressed against a rigid plane. The contact area was negligibly affected in size or shape by the presence of the tangential force of friction, in accord with the theory for the contact of elastic spheres. The deformations of the specimens were, within experimental error, completely recoverable but depended on the time of loading. The effects of changes in the four variables, load, radius, speed, and time were found to be essentially independent. Subsidiary experiments showed that both friction and contact area increased by about 10% for each factor-of-10 increase in loading time in the range 5-1000 sec. and that friction increased by a factor of 3 as sliding speed increased from 10-7 to 3 × 10-2 cm./sec. The main series of measurements (at constant sliding speed and loading time) showed that the dependence on load W of both the contact area A and the friction F could well be represented by the expressions: A = βWm and F = αWn (where α and β were constants for a given specimen). The values of m and n were almost independent of specimen radius and their mean values, for 15 specimens, were 0.708 ± 0.006 and 0.781 ± 0.012, respectively. The difference between these values, 0.073 ± 0.013, is statistically highly significant and in the following paper is interpreted as implying that the friction per unit area of true contact between nylon and glass increases with pressure. The dependence of A on the specimen radius R (which is included in β) was found to be as R0.576. The value of this index of R and the value of m are both consistent with a power-law dependence of mean contact pressure on deformation (measured by the ratio of contact to specimen radius) with index 0.82. The values of α for specimens of the same radius showed too much variation for a useful estimate of the dependence of F on R to be obtained.
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    Polyhydroxyethers. I. Effect of structure on properties of high molecular weight polymers from dihydric phenols and epichlorohydrinPresented at the American Chemical Society, Los Angeles Meeting, March 31-April 5, 1963. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2135-2144 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: An interesting series of high molecular weight thermoplastic polymers, based on dihydric phenols and epichlorohydrin, have been prepared. The polymers have, in common, a structure which can be represented by the general repeating unit where E is a radical residuum from a dihydric phenol. Certain properties appear characteristic of this class of polymers. All contain some chain branching through the secondary hydroxyl group. They are amorphous, noncrystallizable, transparent, tough, and thermally stable. They show two glassy state transitions, a minor transition at about -70°C. and a major transition at a considerably higher temperature. This family of polymers provides an excellent means for studying structure-property correlations. Data are reported showing the effect of the structure of the dihydric phenol moiety (E) on the major glass transition temperature and on certain barrier properties of a series of these polymers. The polymer prepared from 2,2-bis(4-hydroxyphenyl) propane, bisphenol A, is considered typical of this series; its mechanical and physical properties are described in somewhat more detail and compared with properties of certain commercial polymers.
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    Reactions of irradiated polytetrduoroethylene resin (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2121-2133 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Powders and compacted preforms of virgin unmelted polytetrafluoroethylene were subjected to ionizing radiation in high vacuum. The specific gravities, melt Visccmities, and mechanical strengths of the irradiated samples after a standard heating cycle in air or at reduced pressures indicate that degradation is more pronounced in the presence of oxygen than in vacuum. The presence of oxygen in the excessively degraded sample was shown by electron spin resonance and pyrolysis experiments. It is suggested that some branched molecules are also formed on heating the irradiated samples resulting in a broadening of the molecular weight distribution. Primary fluorocarbon radicals of the type . disappear rapidly when heated at 75°C. in vacuum while secondary radicals are stable thermally at 200°C. and disappear only slowly at 400°C. Both typea of radicals react rapidly with oxygen and tetrafluoroethylene at 0°C. The reactions which occur in irradiated polytetrafluoroethylene in various atmospheres and at several temperatures are reviewed in light of the information developed during this research.
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    Polyhydroxyethers. II. Effect of structure on properties of high molecular weight copolymers from dihydric phenol mixtures and epichlorohydrinPresented at the American Chemical Society Los Angeles Meeting, March 31-April 5, 1963. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2145-2152 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The glass transition temperature and gas barrier properties of a number of high molecular weight thermoplastic hydroxyether copolymers have been determined. These copolymers were derived from mixtures of two dihydric phenols and epichlorohydrin. The property data are analyzed in terms of copolymer composition and the random or alternating distribution of monomer units in the polymer chains. In general, the glass transition temperatures of the copolymers were found to be intermediate between the values for the two homopolymers. In one system, good agreement between the experimental data and a simplified equation for the prediction of glass transition temperatures of amorphous, random copolymers was obtained. No differences in the glass transition behavior of random and alternating hydroxyether copolymers could be detected. Gas barrier properties, in general, were found to be intermediate in value between those of corresponding homopolymers. The exceptions are discussed in terms of polymer structure variations.
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    Colorimetric method for measuring polyester degradation due to weathering (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2161-2174 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Chemical changes occurring in thermoset polyesters during exposure to solar and carbon-arc radiant energy were determined quantitatively by a color reaction with a diamine, N,N-dimethyl-p-phenylenediamine, in a methanol-benzene solution. The amount of diamine reacting with a specimen and the color change of the treated specimen, as measured by differential reflectance, varied directly with exposure time. Three commercial polyesters (glass fiber-reinforced) exposed under identical conditions showed widely different degradation rates as measured by the amount of N,N-dimethyl-p-phenylenediamine used per specimen. The relative stability of the three materials was independent of irradiation source. The color of the treated specimen was dependent on exposure time.
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    Polymer structure and gas permeation II. Permeation studies (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2183-2197 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A series of gas permeability studies of plastic membranes demonstrated the strong dependence of gas transport on structural aspects of the membrane. Films of cellulose acetate butyrate, silicone rubber, polyethylene, polypropylene, and vinyl chloride, were used in these studies. The effect of elastic and nonelastic stretching, orientation, plasticization, and phase changes were shown to be detectable by gas permeations. Interpretation of the permeation response, as a function of temperature, is compatible with a thermodynamic appraisal of the permeation process.
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    Polyhydroxyethers. III. Ester derivativesPresented at the American Chemical Society Los Angeles Meeting, March 31-April 5. 1963. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2153-2160 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The esterification of high molecular weight hydroxyether polymers, derived from dihydric phenols and epichlorohydrin, has been studied. The esters of an assortment of monobasic acids, both organic and inorganic, were prepared by reaction of acid halides, anhydrides, esters or free acids with the secondary hydroxyl group in the polymer repeating unit. The effects of the structure of the acid radical and the degree of esterification on polymer properties were determined. In general, esterification resulted in a lowering of the major glass transition temperature of the polymer. This was true at all levels of esterification. Decreased chain symmetry and decreased hydrogen bonding appeared to be the major causes of the observed effect. Permeability of the polymers to oxygen and water vapor was increased by esterification. The increases was found to correlate well with the size and polarity of the acid radical. Some additional properties of the ester derivatives were examined in less detail.
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    Polymer structure and gas permeation. I. Thermodynamic interpretation of permeation (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2175-2182 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A thermodynamic interpretation of the permeation process of gas transport through polymeric membranes is proposed. The mechanism used does not require the usual P = DS relationship. The dependence of gas permeability upon the crystallinity, strain, etc. is presented, and a method for obtaining values for the entropy of crystallization is suggested. Literature data have been correlated by this approach and values for the entropy of crystallization of polyethylene, polyethylene terephthalate, and nylon 610 were derived.
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    The rheological behavior of a filled viscoelastic material (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2211-2216 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The time-temperature superposition principle appears to apply to filled materials, a change in the proportion of filler being equivalent to a shift along the time axis.
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    A study on the thermal degradation of rubber in dilute solutionsCommunication No. 529 from the National Chemical Laboratory, Poona-8, India. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2199-2209 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The kinetics of low-temperature (60-100°C.) thermal degradation of deproteinized and deresinified petroleum ether soluble fraction of natural rubber in two chemically inert solvents, cyclohexane and trans-decalin, have been studied. The changes in Mw, A2, and (r2)1/2 at various stages of degradation have been obtained from the lightscattering data. The rate constants and the energy of activation for chain scission have been calculated from the observed variation in Mu. The scission has been found to be random and the average energy of activation is 25.8 kcal./mole. This low-energy requirement suggests the presence of weak links in the rubber molecule which get ruptured at low temperature.
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    Investigation of the catalyst in the cellulose-DMEU reaction. Part II. Physicochemical studies of the reactionPresented before the Division of Cellulose, Wood, and Fiber Chemistry at the 140th National Meeting of the American Chemical Society, Chicago, Illinois, September 3-8, 1961. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1041-1062 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: In a continuation of a previously reported investigation into the effect of the catalyst in the cotton cellulose-DMEU reaction, experiments were performed in which the four inorganic salt catalysts originally studied, MgCl2, Mg(NO3)2, ZnCl2, and Zn(NO3)2, were employed at the higher metal ion concentration of 0.1M, and CuCl2 and CdCl2 were employed at 0.03M concentration. Data from infrared absorption spectra of the treated cotton products were in agreement with those obtained at the 0.03M catalyst concentration, again indicating that the catalyst entered into the reaction, forming a coordination complex through the formation of nitrogen-to-metal bonds between the catalyst and the DMEU molecule. Similarly, it was again indicated that reaction with DMEU takes place preferentially at the primary alcohol group of the anhydroglucose unit. Analyses of IR data indicated a higher degree of crosslinking, and thus fewer terminal O—H or N—H groups at the 0.03M catalyst than at the 0.1M catalyst concentration. Further evidence of complex formation was obtained from infrared spectra of the product of the CdCl2-DMEU reaction carried out in the absence of cellulose. Supplemental physical data obtained on products of reactions catalyzed with CdCl2 and CuCl2 at the 0.03M level, when compared with those obtained on products catalyzed with MgCl2 and ZnCl2, supported the earlier hypothesis that chlorine damage during heating was dependent upon the ability of the metallic complex to act as a free-radical trap. Additional support for the free-radical mechanism was obtained when treated cloth subjected to chlorination and exposed to ultraviolet radiation suffered the same discoloring and degradative effect as cloth chlorinated and subsequently scorched according to the usual AATCC method. Reaction rates of the cellulose-DMEU reaction at 45, 55, and 65°C. with each of the four catalysts at the 0.03M concentration were determined by following changes both in nitrogen and formaldehyde content as well as in crease recovery properties. The reaction was found to be pseudo first order when followed to 2/3 completion, and the catalysts, when ranked according to greatest to least effect upon the reaction rates, followed the order: Zn(NO3)2 〉 ZnCl2 〉 MgCl2 = Mg(NO3)2. Enthalpies, entropies, and free energies of activation have confirmed the earlier hypothesis that the metal ion enters into the reaction, forming a transition state complex.
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    The mechanism of ozone cracking. I. Ozone cracking of plastic films (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1117-1132 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Stretched films from partly unsaturated natural rubber hydrochloride develop cracks and fracture in ozonized oxygen. Cracking occurs only above a minimum stress level of about 70 kg./cm.2. Ozone sensitivity increases exponentially with stress, but goes through a maximum near the yield point of the thermoplastic films. Contrary to rubbers, these high-modulus materials do not undergo overall stress relaxation prior to fracturing induced by ozone. The rate of surface ozonization of an unstretched film is estimated gravimetrically and volumetrically; it is found to be similar to that of rubber surfaces. Physical and chemical changes of the ozonized surface are reported. Results are briefly compared with ozone attack on other (nonrubber) materials.
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    A study of the oxidative degradation of furfuryl alcohol polycondensates by infrared spectroscopyThis work was supported, in part, under Grant DA-ORD-31-124-60-G51 from the U. S. Army Research Office (Durham). (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1083-1091 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The oxidative curing and oxidative degradation of cured furfuryl alcohol polycondensates was examined, with infrared spectroscopy, by following the functional group changes occurring in the solid phase of the resin. It has been found that the oxidative degradation of nitrogen-cured resins initially proceeds through the oxidation of methylene linkages to bifuryl ketonic species activated by adjacent furan rings. The second stage of oxidation is the scission of the bifuryl ketonic chain positions to produce substituted furoic acids. The process is postulated to proceed in a manner analogous to that observed in phenolic resin systems. The curing of furfuryl alcohol resin in air is shown to be a multistep process in which the initial oxidation of methylol groups to carboxylic acids is competitive with further polymerization through methylol condensation at adjacent furan ring alpha hydrogen positions. In addition, the oxidation of already formed methylene linkages to the bifuryl ketones is a competitive process removing methylene linkages after they are produced during further condensation (curing reactions). These routes of degradation are in good agreement with observed oxidations of furfuryl alcohol resins under more drastic conditions and offer a reasonable mechanism for resin degradation consistent with observations in analogous polymer systems.
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    Some aspeots of the microetructure of polyblends of poly(vinyl chloride) and butadiene-acrylonitrile copolymer rubber with and without talc fillers (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2269-2292 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Fracture and microtome sections of polyblends, prepared from varying proportions of poly(vinyl chloride) and an elastomer (with and without talc fillers) and with the use of different conditions of mixing, were examined with the electron microscope. In general, the structures observed in cut and in fracture sections were very similar when taken from the same polymer at the same reference planes with respect to direction of process-induced orientation. Optimal tensile behavior seems to occur when the degree of mixing establishes a structure resembling a fibrous interweaving of continuous domains. Undermixing or overmixing seems to establish more random dispersions of more or less large and discrete particles of rubber in a continuous poly(vinyl chloride) phase. Introduction of fillers changes the microstructure of the fracture patterns. Particularly in polymers containing talc fillers, the influence of prior strain history on microstructure is very evident. Thirty-eight figures are shown to demonstrate how differences in composition, mixing process, and strain history can alter the microstructure produced by fracture or cutting of the plastic.
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    Polymer flow irregularities (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S27 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Additional Material: 3 Ill.
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    Infrared spectra of irradiated polyethylene (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2307-2318 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The irradiation of polyethylene causes a number of molecular rearrangements in the chemical structure of polyethylene. In addition to the significant changes in the type and distribution of unsaturated groups, an infrared comparison of the radiation induced chemical changes that occur in air and in a vacuum showed that the presence of oxygen has a marked influence on the structural rearrangements that occur on irradiation. The infrared spectra of irradiated single crystals prepared by two different means indicated the location of vinyl groups in the crystals and their protection from radiation by aromatic structures. From these data, a number of reaction mechanisms are postulated which can contribute to our understanding of irradiation effects on polyethylene.
    Additional Material: 9 Ill.
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    Determination of carboxyl groups in the presence of carbonyl groups in oxidized polyolefins by using sulfur tetrafluoride (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2319-2322 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A simple analytical technique has been developed to determine the amount of carboxyl groups present in degraded polyethylene film. This procedure is based upon the relative reactivities of the various carbonyl groups present, in oxidized polyethylene film, to sulfur tetrafluoride gas. The quantity of the carboxyl groups in the film is then measured as a function of the absorption at 5.45 μ.
    Additional Material: 1 Ill.
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    Calibration device for an extensometer (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S15 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/app.1963.070070331
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    Strength of filled rubbers: Temperature, rate, and oxygen effectsThis work was sponsored by the Goodyear Tire and Rubber Company as part of a general program in support of fundamental research on synthetic rubber. A major portion of this work was carried out at the University of Akron and was reported at the Gordon Research Conference on Elastomers, 1961. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1165-1174 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The time taken to break under fixed load has been measured for three SBR-filler systems. Two SBR-HAF black systems were used, one vulcanized with sulfur and the other with dicumyl peroxide; the third system was an SBR-silica formulation. Measurements at several temperatures between 30 and 100°C. allowed the computation of an activation energy for the breaking process: 45 kcal./mole for all three systems. By measuring the tensile strength of the filled stock in air and vacuum at various temperatures, it was shown that the presence of oxygen seriously decreases the strength of the filled stock at high temperatures, an effect not present in the gum stock or in silicasilicone stocks.
    Additional Material: 8 Ill.
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    The glass temperature of asphalt (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S45 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Additional Material: 1 Ill.
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    Introduction of polymer samples into a microreactor (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S19 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/app.1963.070070333
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    Polysaccharide B-1459; a new hydrocolloid polyelectrolyte produced from glueose by bacterial fermentation (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S21 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1963.070070334
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    High gloss of extruded high impact polystyrene sheet. A microscopical study of sheet morphology (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S51 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1963.070070638
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    Quantitative characterization of polybutadiene networks (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1257-1263 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Using a relationship found to be applicable for natural rubber networks in establishing contributions of chemical crosslinking, entanglements, and networks defects to physical crosslinking, a physical versus chemical crosslinking “calibration” is developed for polybutadiene prepared by organolithium initiation. This calibration is then used to determine chemical crosslink yields for sulfur-sulfenamide, thiuram, and peroxide vulcanization. Crosslink yields for polybutadiene in the sulfur-sulfenamide and thiuram curing systems are shown to be similar to those of natural rubber. In peroxide vulcanization the crosslink yield is in excess of unity for polybutadiene. Evidence is presented which indicates that this is due to a polymerization type reaction involving vinyl groups resulting from 1,2-addition during polymerization.
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    Fractionation of acrylonitrile copolymers. I. Development of a methodPaper presented at the 142nd National Meeting of the American Chemical Society, Atlantic City, N. J., September 1962. (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1243-1255 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The mechanism of precipitation of acrylonitrile polymers was investigated using different nonsolvents. The effect of the dielectric constant and the polarity of individual bonds in the molecule of precipitant is discussed briefly. A methyl methacrylate-acrylonitrile copolymer was successfully fractionated from dimethylformamide solution, using a two-stage fractionation technique, and a mixture of (2 parts n-hexane + 1 part ether) as a precipitant. The molecular weight distributions of primary fractions were skewed to the left and overlapped each other. A large, 100-g. sample of the same copolymer was separated into eight primary fractions, which on refractionation gave a result substantially the same as that obtained by the small scale experiment. An experimental terpolymer of methylvinylpyridine-vinyl acetate-acrylonitrile, prepared by suspension polymerization, was carefully fractionated by the same method. The polymer was shown to have a double-peak molecular weight distribution in agreement with the earlier suggestion that acrylonitrile in aqueous suspension polymerizes by two simultaneous mechanisms: (1) homogeneous polymerization of single radicals in solution, and (2) heterogeneous growth of radicals present in stable suspended polymer particles. The above conclusion was further supported by methylvinylpyridine analysis on secondary fractions. It was found that the low molecular weight fractions contained appreciably more of the water-soluble monomer (M.V.P.), than the high molecular weight fractions.
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    Sign reversal of permselective membranes: A possible mechanism for neural conduction (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1265-1271 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: An electrochemical mechanism is sought for to explain the sudden transient change of potential across a nerve membrane during neural conduction. Ion-permselective membranes change the sign of their permselectivity if the charge of their fixed ions is overcompensated for by highly charged counterions which become strongly bound to these fixed sites by electrostatic forces. Imagine a membrane with its sign thus reversed beyond a given borderline: cations could traverse on one side in the vicinity of this line and anions on the other, while no ions would traverse pure membrane faces themselves. Thus concentrations would be equalized at the borderline by passive diffusion, while the sign of membrane potential would change from one side to the other of the border. A mechanism for automatic propagation of the border along the membrane is suggested. Sign reversal of membranes can also be caused by covalent bonding of oppositely charged groups to a charged membrane site, for instance by esterification of a carboxyl group or of a phosphoric acid group of a lipoproteid nerve membrane with the amino alcohol choline. Hydrolysis of such an ester would cause the sign of the membrane to revert to its original direction. Such acetic sites and choline abound on nerve membranes, together with enzymes, which are known to split and synthesize choline esters. Their electrochemical function in neutral conduction might well be this changing of sign of membrane permselectivity.
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    Differential thermal analysis of polymers. II. Melting (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1281-1289 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A theory is presented of the way in which the melting of a polymer is manifested in a differential temperature analysis thermogram. An analytical method based on this theory allows a precise determination of both the melting point and the crystalline weight fraction as a function of temperature. Experimental results for linear polyethylene and crystalline polypropylene confirm the theory.
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    Raman and infrared spectra of 3-methylbutene-1 (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1307-1315 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Infrared and near-infrared spectra of 3-methylbutene-1 were observed for the vapor phase at room temperature. Also, Raman displacements and depolarization factors of 3-methylbutene-1 in methanol and carbon tetrachloride were obtained at the same temperature. Tentative assignments of the observed Raman and infrared bands were made, and a classification of bands on the basis of group frequencies is given.
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    A recording apparatus for the measurement of longitudinal creep (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1273-1279 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A recording apparatus for measuring longitudinal creep was developed to study viscoelastic properties of polymeric films. The heart of the apparatus is a photoelectric transducer that converts specimen extension and contraction into a voltage which is then applied to a millivolt recorder through a d.c. low-drift amplifier. As used in this apparatus, the phototube detects the variable by having its photocathode surface shadowed by a movable mask. Supplementing the recording part of the apparatus is a mechanism for controlling specimen temperature. A polymer of plasticized polyvinyl chloride was studied, to demonstrate the applicability of the apparatus. The results obtained compared favorably with the method of visually observing the displacement with a cathetometer.
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    Temperature dependence of dynamic mechanical properties of mixed polymer systems. II (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1291-1306 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The temperature dependence at constant frequency of the viscous component E2(1/T) of the dynamic modulus has been determined for a homologous series of butadiene-acrylonitrile copolymers supported in a matrix of styrene homopolymer. The results, which agree with those reported earlier for a homologous series of butadiene-styrene copolymers, indicate that the transition temperature of a given plastic homopolymer, as measured from dynamic mechanical properties at essentially constant frequency in the range 200-300 cycles/sec., is depressed by the presence of a copolymerized rubbery diluent as the melting point of crystalline polymers is depressed by the presence of noncrystallizing comonomers. In addition, it has been found that the transition temperature is depressed by the presence of monomeric diluents much as the melting point of crystalline polymers is depressed by the presence of monomeric diluents. Two earlier assumptions, that the dynamic properties in the frequency range of interest should be independent of both the molecular weight of the rubbery copolymer and the degree of dispersion of the copolymer in the thermoplastic matrix, have been subjected to experimental scrutiny. The assumption regarding the dependence on molecular weight has been substantiated, at least for DP's in excess of 100. The assumption regarding the dependence on the degree of dispersion has been negated; the area under the E2(1/T) peak was found to be considerably greater for a coarse dispersion than for a fine one.
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    Measurement of triboelectric position (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1317-1323 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A convenient technique is presented for determination of triboelectric characteristics of a film sample relative to a group of reference surfaces and to other film samples, with the use of inexpensive, easily assembled equipment. It consists of pressing a number of reference surfaces into contact with a test film, determination of the sign and intensities of the charges generated, by spraying with an indicating powder, and estimation of tribo-electric position of the test sample by the distribution of positive and negative charges generated. With this technique, relative triboelectric characteristics were determined for films of various polymers. The measurements give some insight into the relation between polymer structure and triboelectric characteristics.
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    Characteristic viscoelastic parameters for amorphous polymers (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1341-1347 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: By use of a reference value of modulus equal to 109 dynes/cm.2 and a reference value of time equal to 10 sec., characteristic viscoelastic parameters are defined from stress relaxation master curves and from modulus-temperature curves. Values of these parameters are tabulated for several linear amorphous polymers and slightly crosslinked amorphous polymers.
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    Dielectric loss features of some epoxy resins (1963)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2003-2023 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: At temperatures far below the heat distortion point, the dissipation factor (and therefore power factor) of epoxy resins is comparably low - in the order of 0.001-0.01. Internally flexibilized, polyester-modified resins may have higher loss tangents, in the order of 0.01-0.10, even at room temperature. At temperatures far above the heat distortion point, anhydride curing agents give lower dissipation factors than do amines or acids. With anhydride cures, the higher molecular weight resins investigated cure faster than the lower molecular weight resins, give lower elevated temperature power factors and loss tangents, and are tougher. With any hardener-epoxy resin system, the optimum elevated temperature power factor, weight loss on aging and heat distortion point will probably depend on a close examination of the optimum hardener/resin ratio.With certain anhydride-cured low molecular weight epoxy resin systems, an increased rate of cure and lower elevated temperature power factor may be obtained by use of a small amount of higher molecular weight (polyhydroxy) epoxy resin. Attempts to compare the effect on power factor of changing the hydroxyl groups to less mobile dipoles by acetylation were unsuccessful, since the resulting acetoxy groups changed the cure mechanisms. However studies with resins of different molecular weights indicated that the effect of hydroxyl content on elevated temperature power factor is subordinate to other effects such as the rigidity of the cured resin system, rate of cure and ionic impurities. Acetylation of hydroxyl-containing epoxy resins may inhibit cure with some curing agents, due to side reactions of the resulting acetoxy group with specific hardeners.
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    Incremental modification of styrene-butadiene rubber with tert-dodecyl mercaptan (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 116-123 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The molecular weights and molecular weight distribution of a styrene-butadiene rubber produced at 5°C. according to an incrementally modified recipe with tert-dodecyl mercaptan modifier, do not differ significantly from those of similar conventionally modified rubbers. The limiting effect of diffusion upon the mass transfer of mercaptan in the system provides a consistent explanation of this finding.
    Additional Material: 4 Ill.
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    Glass transitions in polymers (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. S1 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051319
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    Polymer news (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. S4 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1961.070051321
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    Use of the HLB system in selecting emulsifiers for emulsion polymerization (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 135-148 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: In the present work a wide variety of nonionic emulsifiers and anionic/nonionic blends of emulsifiers were evaluated in the emulsion polymerization of vinyl acetate and styrene. It was found that the emulsion stability and other polymer emulsion properties are often dependent upon a certain property of the emulsifier known as the HLB value. It has been shown elsewhere that the HLB value can be correlated with a fundamental physical property of the system oil-water-emulsifier, namely, the spreading coefficient of the internal phase liquid on the surface of a 1% solution of the emulsifier in the external phase. In the emulsion polymerization of styrene, good emulsion stability coupled with adequate conversion rate was obtained in an emulsifier HLB range of 13 to 16. For certain emulsifier blends it was found that emulsion viscosity and emulsion particle size were strongly dependent on the HLB of the emulsifier. Similar comments apply to vinyl acetate polymerization, except that the most stable emulsions were obtained with emulsifiers in an HLB range from 14.5 to 17.5. These observations on preferred HLB range apply only to nonionic emulsifiers and anionic/nonionic emulsifier blends, which were the emulsifier types screened in the present investigation. For both styrene and vinyl acetate the most generally satisfactory emulsion properties were obtained in the present work by the use of an anionic/nonionic emulsifier blend (G-3300/G-3920).
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    Influence of the initiator on the grafting of polyvinyl polymers (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 149-152 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The dependence of grafting on the type of initiator has been examined in the case of three polymer-monomer systems: polystyrene-methyl methacrylate, polymethyl methacrylate-vinyl acetate, and polyethyl α-chloroacrylate-vinyl acetate. The different initiators used in these experiments were benzoyl peroxide (Bz2O2), azobisisobutyronitrile (AIBN), di-tert-butyl peroxide (DTBP), and tert-butyl hydroperoxide (TBHP). In each case the graft copolymers were separated from the homopolymers by fractional precipitation or by extraction. In the case of the system polystyrene-methyl methacrylate, an appreciable degree of grafting as well as formation of graft copolymer occur in the presence of Bz2O2; in contrast, the grafting is low with DTBP and doubtful with AIBN. For the other two systems no noticeable differences occurred as function of the initiator. In the case of polyethyl α-chloroacrylate the amount of graft copolymer is exceptionally high owing to the sensitivity of this polymer to a radical attack; this sensitivity results in the partial insolubility of the graft copolymers in the presence of TBHP and DTBP, but not in the presence of AIBN.
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    A new synthetic elastomer based on a chlorophosphonated polyolefin (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 157-162 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A new synthetic elastomer has been obtained based on an ethylene-propylene copolymer prepared using an organometallic catalyst system. Reactive sites (phosphonyl dichloride groups) are placed on the copolymer chain by treating the polymer with phosphorus trichloride and oxygen. After hydrolysis or alcoholysis of the phosphonyl dichloride groups to phosphonic acid or phosphonic acid esters, vulcanization may be carried out by reaction with metallic oxides, particularly lead oxide. Vulcanizates of the polyolefin elastomer have outstanding resistance to heat, ozone, and oxygen, and have excellent electrical properties. This combination suggests the use of this material in high temperature electrical applications.
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    Changes in fine structure and mechanical properties induced by cyanoethylation of cotton yarns. II. Reacted without longitudinal shrinkagePaper presented before the 138th Meeting of the American Chemical Society, New York, September 11-16, 1960. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 163-170 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The cellulose of cotton yarns was reacted with acrylonitrile under conditions preventing their longitudinal contraction. Changes taking place in the fine structure of the fiber were studied by means of optical microscopy, density measurements, x-ray diffraction, and thermal stress behavior measurements. The results indicate that in spite of the strong tensions developed in the yarns, the reaction proceeds in both the accessible and the crystalline regions with considerable volume expansion and eventual disappearance of crystalline structure. Suggestions of a glass transition temperature appear at substitutions slightly above D.S. = 1. Annealing becomes possible at substitutions above D.S. = 2 with the development of the cyanoethyl cellulose crystal structure and over 40% increase in tensile strength. Changes in tenacity, ultimate elongation, energy of rupture, and immediate elastic recovery were also observed.
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    Poly(4-methyl-1-pentene) and some soluble crystalline copolymers (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 184-190 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Poly(4-methyl-1-pentene) has been prepared by polymerizing the monomer over a catalyst made from titanium tetrachloride and lithium aluminum tetradecyl. The molecular weight of the crystalline polymer was invariably too high for fiber preparation, even when polymerization variables were varied drastically, so a technique for thermal cracking was developed. By heating grease-free, crystalline poly(4-methyl-1-pentene) in a vacuum at about 280°, it was possible to lower smoothly the molecular weight of the polymer to any desired value, without undesirable crosslinking or by-product formation. The polymer was melt-spun by conventional techniques to highly oriented, tough fibers. Copolymerization of 10-25% 1-hexene and other linear 1-olefins with 4-methyl-1-pentene gives products which are still high-melting, but which are readily soluble in such solvents as cyclohexane or chloroform, in contrast to the homopolymer which is only slightly soluble. Polymerization in solvents for the copolymer gave solutions which were converted to fibers and film without intermediate isolation of polymer or removal of the catalyst. An interesting terpolymer in which divinylbenzene was the third component was found to be initially soluble, but was readily crosslinked at elevated temperature.
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    Structural characterization of vulcanizates. Part II. Use of triphenylphosphine to determine the structures of sulfur linkages in unaccelerated natural rubber-sulfur vulcanizate networks (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 299-302 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Treatment of unaccelerated natural rubber-sulfur vulcanizate networks with triphenylphosphine in benzene at 80°C. effects the removal of part of the combined sulfur, the proportion removed decreasing with increasing cure time. This partial desulfurization of the network is attributed, on the basis of the mode of interaction of simple organic di- and polysulfides with triphenylphosphine, to the conversion of polysulfide linkages in the network into either mono- or disulfide groups. Knowledge of the amount of sulfur removed by the reagent, and of the chemical degree of crosslinking and combined sulfur content of the untreated networks permits the following semiquantitative conclusions to be reached concerning the structures of the sulfur linkages in the networks: (1) long polysulfidic crosslinks (—S11— to —S12—) are initially formed, which on continued cure progressively decrease in length to a limiting value of —S2— to —S4—; and (2) a very high proportion to the combined sulfur (ca. 77% for short cure times, increasing to ca. 95% on extended cure) is present in cyclic monosulfide groups situated along the polyisoprene chains.
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    The relationship between glass temperature, molar cohesion, and polymer structurePresented before the Division of Polymer Chemistry at the 138th meeting of the American Chemical Society, New York, September 1960. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 318-321 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: An empirical equation relating glass temperature, molar cohesion, and polymer structure has been developed from data found in the literature. A fairly extensive list of group cohesion values has been obtained from this relationship and glass temperatures which are in good agreement with reported values have been calculated. The equation is $$ H_c = 0.5nRT_g - 25n $$ where Hc is the molar cohesion and n is an empirical number obtained from the polymer structure.
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    Isobutylene copolymers of vinylbenzyl chloride and isopropenylbenzyl chloride (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 452-459 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The styrene derivatives vinylbenzyl chloride and isopropenylbenzyl chloride were prepared and copolymerized with isobutylene and propylene in order to produce polymers with reactive halogens. Vinylbenzyl chloride and isobutylene have relative reactivities such that the copolymer is much richer in isobutylene than the starting mixture, while with isopropenylbenzyl chloride and isobutylene the difference in reactivities is less and is in the opposite direction. Copolymers containing small amounts of the reactive benzylic chlorine were vulcanized, either with amines or with a conventional butyl rubber cure. Permselective membranes were prepared from copolymers rich in benzylic chlorine.
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    The mechanism of post cure of viton ARegistered trademark of E. I. du Pont de Nemours & Co., Inc. Fluorocarbon elastomerBased on a lecture delivered at the 2nd International Synthetic Rubber Symposium, London, October 1960, by arrangement with Rubber and Plastics World. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 460-467 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The necessity for oven post-curing Viton A vulcanizates is explained in the following way: The formation of crosslinks is accompanied by the elimination of HF from the polymer. In the subsequent reaction of HF with the magnesium oxide present as acid acceptor water is formed which acts to inhibit the full development of cure unless it is removed from the vicinity of the polymer by post-curing in an open system. Measurement of the rate of elimination of water from the polymer serves as a method of following the development of crosslinking during cure. Approximately two moles of water, derived from four moles of hydrogen fluoride, are associated with the use of one mole of diamine curing agent. This ratio is confirmed by independent estimates of the relationship of crosslinking density to curing agent level based on measurements of swollen compression moduli.
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    Room temperature sulfur and nonsulfur vulcanization of natural rubber: With sulfur and piperidinium n-pentamethylenedithiocarbamate and with quinone dioxime (GMF) and yellow mercuric oxide (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 349-353 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Calendered sheets of pale crepe rubber containing an ultra-accelerator, piperidinium N-pentamethylenedithiocarbamate, and zinc oxide were embedded in powdered sulfur and kept at room temperature. Tensile strengths up to 294.2 kg./cm.2 (4185 psi) and elongations up to 530% were attained; the combined sulfur in 115 weeks was 3.60%. Calendered pale crepe rubber containing 10 parts of yellow mercuric oxide to 100 parts of rubber allowed to stand covered with quinone dioxime (GMF) powder at room temperature slowly vulcanizes, reaching a tensile strength of 53.1 kg./cm.2 (754 psi) in 405 days, and retaining this condition for at least twice this same period of time. The elongation reached 740%, and the set was 0.16. The tensile strength obtained is almost as high as that obtained in a press cure with quinone dioxime alone. The untreated sample containing yellow mercuric oxide alone showed a tensile strength of only 5.3 kg./cm.2 (75 psi). Calendered pale crepe with no mercuric oxide set in quinone dioxime and calendered pale crepe containing 2 parts of quinone dioxime, when allowed to stand at room temperature, showed no signs of vulcanization.
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    Uniformity of substitution during the emulsion xanthation of celluloseA portion of a thesis submitted in partial fulfillment of the requirements of The Institute of Paper Chemistry for the degree of Doctor of Philosophy from Lawrence College, Appleton, Wis., June, 1960. This work was carried out under the direction of Kyle Ward, Jr. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 364-369 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Viscose-grade cotton linters (DPw = 1135) were converted to viscose by the emulsion xanthation technique. Two variables - namely, substitution level and xanthation time - were considered insofar as their influence on the uniformity of substitution with regard to chain length was concerned. The stable diethylacetamide derivatives were prepared by reaction with diethylchloroacetamide and fractionally precipitated from aqueous 2-chloroethanol. The DPw and degree of substitution (DS) of the individual fractions were determined. The results in each case indicated that the longer chains were more highly substituted than the shorter chains. For a constant xanthation time (6 hr.), uniformity in substitution improved with increasing substitution level. For a constant CS2:cellulose ratio (1.48), uniformity increased with xanthation time. A mechanism is suggested which accounts for these phenomena.
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    A comparison of the thermal gradient and elution methods of polymer fractionation (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 354-363 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The elution method is essentially a single-stage process, whereas the thermal gradient method is a multistage process which depends upon a thermal gradient to bring about reprecipitation of polymer in the fractions. As a test of the effectiveness of the thermal gradient, comparisons have been made of fractionation by these two column methods on high molecular weight polystyrene samples. It was found that the thermal gradient method definitely provides superior resolution and reproducibility, as expected. However, the degree of fractionation obtained by the elution method was surprising, accounting for at least 80% of the sample under the usual conditions and giving complete fractionation with certain modifications of conditions. These results indicate the difference in performance of the two methods is less than expected from an elementary consideration of the operation of the columns, and fractionation by the elution method, as conducted here, exceeds that expected for a single-stage extraction process. Although the reasons for the observed behavior are not clear, the following conclusions have been reached about certain factors which influence fractionation. Alternative methods of controlling the concentration of polymer in the fractions give almost equivalent results but enhanced resolution of the high molecular weight portion of the sample is obtained with extended solvent gradients. The inhibitor, tert-butyl catechol, which it was necessary to add to the solvents to limit degradation of the very high molecular weight sample, plays a specific role in the fractionation due to a reaction with the polystyrene which alters the fractionation behavior without affecting the molecular weight. Also, trace amounts of chemical heterogeneity in the polymers, presumably hydroxyl groups, have a marked adverse effect on fractionation by the elution method and probably account for molecular weight reversals observed in some fractionations by the thermal gradient method. It is suggested that adsorption on the surface of the beads is responsiblp for the adverse effect of chemical heterogeneity on the fractionation and that possibly an adsorption which increases with molecular weight contributes to fractionation by the elution and thermal gradient methods.
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    Effects of by-products, trace components, and similar compounds in viscose on ripening (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 375-383 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The effects on viscose ripening of a variety of materials are reported. (1) Normal constituents (Na2CO3, Na2CS3, NaCl) appeared not to affect ripening; however, Na2S retarded ripening. By-product removal appeared to retard ripening. (2) Oxidizing agents (H2O2, Na2Sx) accelerated ripening; reducing agent (Na2SO3) retarded ripening; this is suggestive of possible addition product formation. (3) Na2SO4, (CH3)2SO, KClO3, Na2BH4 showed no effect on ripening. (4) Salts which precipitated as hydroxides or carbonates did not appear to affect ripening. (5) Salts which formed insoluble sulfides resulted in an initial increase in ripening rates. In later stages, ripening proceeded normally, probably after the salts were removed from solution as insoluble sulfides. (6) FeCl3, BiCl3 and Na3AsO3 appeared to retard ripening. (7) A comparison of the effect on ripening of the trivalent state of elements in group V of the periodic table showed that the rate of ripening decreased with the oxidation potential of the element. (8) The addition of sodium zincate retarded ripening and suggested possible cross-linking of xanthate and by-product sulfur, or of two xanthate groups. (9) Addition of tin and chromium salts at the 0.5% level resulted in gelation of the viscose within 30 min. after the addition.
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    Radiation crosslinking of vinyl chloride-vinyl stearate copolymer (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 388-396 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The crosslinking of internally plasticized polyvinyl chloride-stearate copolymer by irradiation with high-energy electrons was studied. Based on gel yields and swelling as a measure of relative crosslinking, the effect of added tetra-functional monomers, and of carbon black and silica fillers are discussed. Crosslinking by dicumyl peroxide a t 170°C. even in the presence of a stabilizer, causes concurrent decomposition (dehydrochlorination) which is avoided in the radiation-crosslinking process. The heat stability of the copolymer is not impaired by radiation crosslinking under the proper conditions. Results of tensile measurements a t 25 and 150°C. are given for the radiation-crosslinked copolymer with and without filler reinforcement.
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    Studies on the γ-irradiation of natural rubber latex. The effects of organic halogen compounds on crosslinking by γ-irradiation (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 401-407 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: As the accelerating effect of water in the crosslinking reaction of rubber in natural latex by γ-irradiation was assumed to stem from the decomposition of water into radicals by γ-irradiation, more effective reagents were sought among the organic halides which have greater G values for radical formation by γ-irradiation and, simultaneously, an affinity for rubber greater than that of water. 1,2-Dichloroethane, chloroform, carbon tetrachloride, and benzene (for comparison) were tested, and these compounds, except for benzene, were found to accelerate the reaction in proportion to their G values for radical formation. Benzene was found to have no effect, in concentrations between 1 and 5 phr. The optimum dosage was decreased to 2.1 × 106, 1.0 × 106, and 7.6 × 105 r by the addition of 1, 3, and 5 phr of carbon tetrachloride, respectively, and was assumed to have decreased to 1.17 × 107, 9.0 × 106, and 7.6 × 106 r with 1, 3, and 5 phr of 1,2-dichloroethane, and to 8.6 × 106, 6.2 × 106, and 5.2 × 106 r with 1, 3, and 5 phr of chloroform, respectively. The physical properties of the films obtained at the optimum dosages under these accelerating conditions were equal to those of the latex irradiated up to the optimum dosage with no addition of halide. No side reactions occurred during the halide-accelerated crosslinking that were sufficiently extensive to influence the infrared spectra.
    Additional Material: 15 Ill.
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    The estimation of catalytic parameters of metal acetylacetonates in isocyanate polymerization reactionsContribution No. 202. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 424-427 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The polyaddition process involving a hydroxy-terminated linear polyester and an organic diisocyanate in the presence of a series of metal acetylacetonates has been investigated. The method involved kinetic analysis of plasticity build-up in a Brabender Plastograph. Catalytic orders and relative catalytic constants (kc/k0) were determined for Mn(Aa)3, VO(Aa)2, V(Aa)3, Fe(Aa)3, Cu(Aa)2, Co(Aa)3, and Cr(Aa)3; the constants decrease in that order. Catalytic orders are unity for all complexes save manganese, which is 1.75. No correlation between dissociation potential and catalytic coefficient has been found, and it is believed that catalysis may be associated with the paramagnetic properties of the metal.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051607
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    The strain dependence of rubber viscoelasticity. Part III. Natural and butyl rubber at high extensions (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 428-435 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dynamic Young's moduli are derived from observations of wave propagation in stretched filaments of natural and butyl rubbers. Extensions up to about 700% are studied within a temperature range of -45 to +50°C. and a frequency range of 0.2 to 20 kycles/sec. At constant temperature and frequency both the real (E') and imaginary (E″) components increase with increasing extension. The loss factor (E″/E') decreases with increasing extension, but the decrease is more pronounced for the butyl rubber so that the large difference in damping between the two polymers in the unstrained state is greatly reduced at high extensions. Approximate relaxation spectra are derived for the strained materials on the basis of several assumptions regarding the applicability of the WLF equation. It is found that the spectra are displaced in the direction of longer times by increasing extension; this is equivalent to an increase in the monomeric friction coefficient with extension. The effect is more pronounced for the natural rubber than for the butyl, and consequently the ratio of the friction coefficients (butyl:natural) falls from several hundred unstrained state to approximately 3 at 550% extension.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051608
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    Viscoelastic factors in the strength of elastomers under complex stress by a puncture methodPresented at the Tenth Canadian High Polymer Forum, Ste. Marguerite, Quebec, September 7-9, 1960.Contribution No. 262 from the research laboratory of the Goodyear Tire & Rubber Company. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 442-451 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Investigations of the viscoelastic aspects of the mechanical behavior of polymers have been limited almost exclusively to relatively simple conditions of homogeneous stress, that is, to tension or shear loadings. In the present work a study has been made from the viscoelastic standpoint of the response of several elastomers to a much more complex type of stress distribution arising from penetration up to failure by a cylindrical indentor for a range of temperatures and rates of penetration. The failure or “puncture point” was determined by a dip in the recorded curve of load versus depth of penetration. The puncture strength values were reduced to 25°C. by applying the ratio of absolute temperatures and plotted against the logarithm of the reciprocal of the rate of penetration. These curves were then shifted on the time scale to give a master curve after the manner of Tobolsky and of Ferry. The logarithms of the shift factors thus obtained were related to the reciprocal of the absolute temperature over the range studied. The results indicate a broader generality for the viscoelastic principle of time-temperature equivalence than has usually been supposed.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051610
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    Status of investigations for improving weatherability of linear polyethylene and copolymers (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 612-619 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In an attempt to extend the outdoor serviceability of items molded from linear polyethylene and copolymers, three ultraviolet absorbers, namely, Cyasorb UV-9 (2-hydroxy-4-methoxybenzophenone), Cyasorb UV-314 (2,2′-dihydroxy-4-n-octoxybenzophenone), and TBS (4-tert-butyl phenyl salicylate), sixteen different pigments, and combinations of both ultraviolet absorber and pigment were investigated. Injection-molded test specimens were employed in this study. The laboratory source of radiation to which these samples were exposed was an Atlas XW Weatherometer. Similar samples also were exposed at various outdoor locations including Phoenix, Arizona, Summit, New Jersey, and Newark, New Jersey, to utilize practical conditions of outdoor weathering. During these weathering studies surface cracking was observed as occurring at approximately the same time as a significant decrease in tensile strength, elongation, and melt index. Such observations became a method of rapidly screening a large number of formulations for resistance to ultraviolet radiation. For optimal outdoor serviceability with respect to retention of elongation, tensile strength, and melt index properties of molded items, the following steps are necessary. A high-density resin having as low a melt index as possible is selected. The molded item is designed to minimize the formation of molded-in stresses and strains. Proper selection of UV absorbers, pigments, and combinations of both are made. Pigments such as green, orange, peacock blue, monastral purple, red, and black, in high concentrations, will prolong the outdoor weatherability of a given product.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051717
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    Viscoelastic properties of regenerated cellulose sheet (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 647-654 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The viscoelastic properties of regenerated cellulose containing several different softeners or water only were investigated. Measurements of creep and Young's modulus were made on the Instron tensile tester, and the creep curves were fitted to a mechanical model consisting of Voigt and Maxwell elements of springs and dashpots in series. The elastic and viscous parameters were determined for the various softened films and compared with each other and with measurements of Young's modulus. It was found that the elastic modulus is a function of the effective molar concentration of the softener in the film which is related to its ability to break hydrogen bonds. The inelastic deformation was found to be a linear function of the heat of vaporization of softener (including water) in the film which is related to hydrogen-bonding energy. Thus, inelastic deformation requires breaking of interchain hydrogen bonds in contrast to pure elastic deformation which involves stretching of hydrogen bonds. A relationship of the Voigt unit and of the Maxwell unit on the composition of the cellulose-softener system and on cellulose-softener interaction has been demonstrated.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051806
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    Polysaccharide B-1459: A new hydrocolloid polyelectrolyte produced from glucose by bacterial fermentationPresented before the Division of Carbohydrate Chemistry at the 136th National Meeting of the American Chemical Society, Atlantic City, September 1959. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 519-526 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The exocellular polysaccharide fermented from glucose in good yield by Xanthomonas campestrìs NRRL B-1459, has been characterized. The general aspects of chemical constitution have been established, as well as the physical properties related to practical applicability. This macromolecular polysaccharide is composed of D-mannose, D-glucose, D-glucuronic acid (as the potassium salt), and a small proportion of acetyl groups. It can be produced on an industrial scale and is stable is storage. Analytical fractionation indicates fairly sharp molecular distribution for the native polysaccharide. The polysaccharide forms homogeneous dispersions in water which show plastic rheological properties and viscosity comparable with that of high-grade plant gums. Outstanding characteristics of practical significance are the atypical insensitivity of solution viscosity to salt effects and to heat, especially when salt is present. Solutions of low concentration show a restricted viscosity decrease upon salt addition; those of higher concentrations show substantial increases. Viscosity is enhanced still further by monovalent cations at basic pH and by divalent cations at neutral or slightly basic pH. Salt moderates or eliminates any viscosity decrease due to heat and, in somewhat higher concentrations, it increases the viscosity of heated solutions. Heating or deacetylating Polysaccharide B-1459 causes no impairment of its properties, but actual improvement. The constitutional basis for these unusual properties is discussed.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051704
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    Digital recording and automatic computation of film tensile stress-strain dataPresented at ASTM Committee D-20 Meeting, Detroit, Michigan, October 3, 1960. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 527-533 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A system is described for automatic collection of stress-strain data for polymeric films on magnetic tape for subsequent automatic data reduction and computation of a variety of stress-strain parameters. Two shaft analog-to-digital encoders attached to a conventional tensile tester feed digital information to an incremental pulse recorder which stores all stress and strain data in two channels on 0.625-in. magnetic tape. Specimen information and test constants are inserted by the operator through a keyboard located at the tensile tester. The tape is subsequently fed into a standard digital computer through a special incremental pulse magnetic tape reader. The data pulses are internally stored and converted by means of a special program into eight significant stress-strain parameters for polymeric film samples, plus averages and standard deviations for groups of replicate determinations. These parameters include: corrected length of specimen, initial maximum tensile modulus, offset yield stress, strain at break, strain at maximum stress, maximum tensile stress, tensile stress at break, and work to break. While the program described applies to polymer film testing, both it and the digital recording equipment accessories are applicable with suitable modification, to any analog experimental data. Significant savings in man-hours and increased information output result from use of this system.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051705
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    Effects of heterogeneous acetylation and methylation on mechanical properties of isotropic cellulose film (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 545-552 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects on mechanical properties of heterogeneous acetylation and methylation of isotropic cellulose films have been studied. The effects on breaking load, extensibility, yield point, elastic recovery, and initial Young's modulus in the air-dry state were very small. It is concluded that these properties are not markedly influenced in cellulose derivatives by variation of the nature of the intermolecular cohesive forces in the way that might have been anticipated from the analogy of a simple molecular network. It is suggested that the lack of effect of such treatments, and also the cause of the low elastic recovery in cellulose and its derivatives, may be connected with molecular stiffness, dipole distribution, and supracrystalline structure. Cellulose and its derivatives are contrasted with nylon in this respect. The effects of methylation or acetylation on mechanical properties in water are much more extensive and are attributed to a solubilizing effect which, in the case of progressive acetylation, is ultimately opposed by the formation of acetate-acetate intermolecular bonds that are relatively stable to water.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051708
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    Heterogeneous polymer systems. I. Torsional modulus studies (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 580-588 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Torsional modulus-temperature data have been obtained on heterogeneous polymer compositions prepared by several procedures. Both the state of aggregation of the component chain molecules and their degree of compatibility are significant variables. Modulus curves similar to those for crystalline polymers can be obtained from incompatible polymers having glass temperatures sufficiently far apart. Detailed interpretations are presented for modulus curves of both individual homopolymers and bicomponent heterogeneous polymer mixtures.
    Additional Material: 8 Ill.
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    Grafting of vinyl monomers onto crosslinked polymers. I. Grafting of methyl methacrylate onto fibers spun from polymer blends of polyvinyl alcohol and its partially N-methylolcarbamoylethylated productsPresented at a meeting of the Chemical Society of Japan, Tokyo, October 19, 1960. (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 563-573 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Improvements in physical properties of polyvinyl alcohol fibers were attempted by means of both crosslinking and graft copolymerization. By using the ceric iron redox system on synthetic fibers spun from polymer blends containing polyvinyl alcohol (PVA) and its partially (about 15 mole-%) N-methylolcarbamoylethylated products (PVM) in which the blend ratios were 0/100, 10/90, 15/85, and 20/80 by weight, methyl methacrylate (MMA) was grafted at 30°C. in the aldehyde-free acetone-water system after crosslinking by heat treatment or successive acid treatment. Grafting increases with increasing PVM component. This may be ascribed to the coarsening of the fiber texture caused by polymer blending and the increasing of methylol groups as a reducing agent. Moisture regains decrease with increasing graft fraction, but these appear to be greater than the additive values of backbone and graft polymer. Less shrinkage in boiling water is obtained with the increase of PVM component and grafting; the decreased shrinkage is significant in the acid-treated PVM-PVA fibers, and it reaches a nearly sufficient value at about 50% graft-on. The PVA fibers do not give sufficient shrink-proofing. The inherent tenacity and elongation of the grafted fibers increase slightly with increasing graft-on or denier except at the high grafting above about 100, 150, and 300 in the PVA, acid-treated, and acid-untreated PVM/PVA fibers, respectively; whereas the tensile strength in grams/denier decreases with grafting. Although at high grafting, a destruction in the fiber texture will perhaps occur, the coarser the texture of backbone fiber, the harder the change by grafting. The knot/normal ratios in tensile strength or elongation of the grafted fibers have been retained at above 90%. The elastic recovery of the grafted fibers is considerably improved as compared to the conventional Vinylon fibers. The improvements in the acid-treated and grafted PVM/PVA (20/80) fibers are significantly greater above and below 50% graft-on, especially in the range of lower extension. As expected, the thermosetting property is also appreciably imparted with grafting. In the conventional Vinylon fibers, the formalization for shrink-proofing is usually at a sacrifice of elastic recovery. But MMA grafting in the PVM/PVA fibers gives a fairly good elastic recovery and less shrinkage in addition to thermosetting property, making the most of the characteristics in the longer intermolecular crosslinkages formed between methylol groups or PVA-OH groups and methylol groups.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/app.1961.070051711
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    International rubber conference (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 620-620 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1961.070051718
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    Symposium on structure and properties of regenerated cellulosePresented before the Division of Cellulose Chemistry, at the 139th Meeting of the American Chemical Society, St. Louis, Missouri, March 21-30, 1961 (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 621-623 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1961.070051801
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    The resilience of chemically modified cottons. II. Reactions of cellulose with formaldehyde under acid conditions (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 704-713 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study has been made of the reactions of cellulose with formaldehyde under acid conditions, where the fabrics are baked at elevated temperature. These treatments have involved cotton cellulose in a “dry” or relatively unswollen state and have resulted in the treated fabrics exhibiting improved crease rccovery both dry and wet. It has been found that boiling 1% acetic acid solution reduces the acetal contents of the treated fabrics and causes corresponding decreases in both dry and wet crease-recovery improvement. The reproducibility of these treatments, with respect both to extents of formaldehyde incorporation and to dry and wet crease recovery, is found to be very good within a single treatment and, more importantly, tietween different treatments carried out under the same conditions. The rates of acetal removal by the boiling 1% acetic acid and the relationships between acetal content and crease-recovery improvement have been found to be fairly complex. A study has also been made of the rates of acetal removal by boiling 1% acetic acid for samples of cotton card sliver treated with acid and subsequently heated in sealed tubes with paraformaldehyde. The rates of acetal removal in this case have been observed to be qualitatively similar to those observed for treated fabrics. The implications of these findings are discussed.
    Additional Material: 6 Ill.
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    Polymer news (1961)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 5 (1961), S. 753-753 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1961.070051818
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    Das Schweißen der Nichteisenmetalle, Band 1 : Das Schweißen der Nichteisenmetalle unter Argon. Unter Mitarbeit von M. Kiesche und K. Paul. W. Gilde. 276 S., zahlr. Abb. und Tab. VEB Verlag Technik, Berlin 1961. Preis: DM (Ost) 25,- (1963)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 14 (1963), S. 58-58 
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    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19630140125
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    Nachrichten (1963)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 14 (1963), S. 64-64 
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    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19630140130
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    Kurzreferate zu den Originalarbeiten (1963)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 14 (1963), S. I 
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    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/maco.19630140132
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    Über den Mechanismus des atmosphärischen Rostens des Eisens (1963)
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 14 (1963), S. 69-80 
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    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Im ersten Teil der Untersuchung wurde 1,5 Jahre lang in jedem Monat („Monatsversuche“) und auch in längeren Versuchen festgestellt, wieviel Schwefeldioxyd rostendes Eisen aus der natürlichen Luft aufnimmt und in welchem Verhältnis dieses Schwefeldioxyd zu dem entstandenen Rost steht. Dabei wurde gefunden: Die von rostendem Eisen aus der Luft aufgenommene Schwefeldioxydmenge betrug (in g/m2 · Tag) berechnet) im kalten Halbjahr 60 bis 140%, im warmem Halbjahr 103 bis 120% derjenigen Schwefeldioxydmenge, die von sodagetränktem Filtrierpapier aufgenommen wurde.Im Winter war die von dem rostenden Eisen täglich aufgenommene Schwefeldioxydmenge etwa viermal so groß als im Sommer.Je aufgenommenes Schwefeldioxyd-Molekül rosteten im Winter etwa 15 bis 20, im Sommer etwa 30 bis 40 Atome Eisen. Im Winter war jedoch wegen der etwa viermal so großen Schwefeldioxyd-Aufnahme die Verrostung etwa doppelt so rasch als im Sommer.
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    URL: http://dx.doi.org/10.1002/maco.19630140203
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